CN103014349B - Process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride) - Google Patents
Process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride) Download PDFInfo
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- CN103014349B CN103014349B CN201210546124.0A CN201210546124A CN103014349B CN 103014349 B CN103014349 B CN 103014349B CN 201210546124 A CN201210546124 A CN 201210546124A CN 103014349 B CN103014349 B CN 103014349B
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- bismuth
- biocl
- gas mud
- reclaim
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Abstract
The invention relates to a process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride). The process comprises the following steps: taking the gas sludge, and soaking in coking residual ammonia wastewater; adding Mg powder into the soaking system, and replacing metal impurity elements having poorer activity than that of the MG powder into corresponding simple substances to be filtered and eliminated; heating so as to convert the magnesium element and the zinc element in the system into MgCO3 or ZnCO3 to be deposited, filtered and eliminated; adding cold rolling waste acid, eliminating the lead element through a PbSO4 deposit form, leaving metal impurity elements which are easy to be dissolved as acid in an ion manner, and leaving the bismuth element in a Bi3+ form; adding cold rolling alkali waste so as to correspondingly deposit and precipitate the metal impurity ions including Fe2+, Fe3+, Mn2+ and Mn4+; adjusting the system pH within 1.5-2.1, carrying out cohydrolysis of C1- and Bi3+ in the system so as to generate BiOCl deposit, and treating the BiOCl deposit so as to obtain the BiOCl. The process is low in cost, and bismuth can be economically recycled from gas sludge to prepare the BiOCl.
Description
Technical field
The invention belongs to solid waste utilization of resources field, be specifically related to a kind of technique that bismuth is prepared BiOCl that reclaims from gas mud.
Background technology
Whole nation iron and steel yearly capacity surpasses 1.40 hundred million tons, and steel smelting procedure produces gas mud every year up to 2,000,000 tons.In gas mud, be rich in the valuable metals such as iron, zinc, bismuth, lead, manganese, if can not reasonably be used, can have caused disadvantageous effect to environment.Except this, coking production technique can produce a large amount of remained ammonias, and cold-rolling process can produce a large amount of spent acid and salkali waste.If can make good use of preferably these several waste resources, will all play an important role to the utilization of steel industry changing waste into resources and environmental protection.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of technique that bismuth is prepared BiOCl that reclaims from gas mud.It is with low cost, can very economically from gas mud, reclaim precious metal bismuth and make BiOCl.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
From gas mud, reclaim bismuth and prepare a technique of BiOCl, it is characterized in that: it comprises the following steps:
(1) get gas mud, add remained ammonia that coking process produces soak to dissolve can and NH
3the impurity element of complexing comprises Cu, Ag, Ni, Co;
(2) in above-mentioned immersion system, add Mg powder, the ammonia complex that comprises Cu, Ag, Ni, Co than the metallic impurity elements of its poor activity is replaced into corresponding simple substance form by replacement(metathesis)reaction, remove by filter;
(3) heating, makes the corresponding MgCO of being converted under the acting in conjunction of magnesium elements in system and zinc element bicarbonate of ammonia in residual coking ammonia water
3or ZnCO
3precipitation forms, removes by filter;
(4) spent acid that adds cold-rolling process to produce, makes lead element in system with PbSO
4precipitation forms is removed, and makes solublely in system for sour metallic impurity elements comprises that ferro element is corresponding with manganese element, with ionic species, to exist simultaneously, comprises Fe
2+, Fe
3+, Mn
2+, Mn
4+deng, make bismuth element with Bi
3+form exists;
(5) salkali waste that adds cold-rolling process to produce, makes the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+etc. corresponding Precipitation, remove by filter;
(6) regulation system pH is 1.5 ~ 2.1, makes the Cl in system
-and Bi
3+common hydrolytic action generates BiOCl precipitation, aftertreatment and get final product.
Press such scheme, the needed remained ammonia amount of described every 1Kg gas mud is 4 ~ 6L, soaks duration and is at least 30min.
Press such scheme, the needed Mg powder content of described every 1Kg gas mud is 6 ~ 12g.
Press such scheme, described step (3) is 80 ~ 120 ℃ for system is slowly heated to system temperature, keeps 30 ~ 50 min, so that the corresponding MgCO that is converted into of the magnesium elements in system and zinc element
3or ZnCO
3precipitation forms, removes by filter.
Press such scheme, the consumption of the spent acid that the needed cold-rolling process of described every 1Kg gas mud produces is 2 ~ 4L.
Press such scheme, the consumption of the salkali waste that the needed cold-rolling process of described every 1Kg gas mud produces is 2 ~ 4L.
Press such scheme, the pH adjusting agent in described step (6) is nitric acid or hydrochloric acid, is preferably hydrochloric acid.Preferably use hydrochloric acid can make the Cl in system
-concentration increases, thereby is easy to Cl in system
-and Bi
3+biOCl precipitation is separated out in common hydrolysis.
Press such scheme, described gas mud is blast furnace gas mud.
The present invention by gas mud, add remained ammonia that coking process produces soak with first can and NH
3the metallic impurity elements of complexing comprises that Cu, Ag, Ni, Co are converted into ammonia complex form, then add active more active Mg the ammonia complex of aforementioned Cu, Ag, Ni, Co Element generation can be replaced into simple substance form and remove, then by under the existence effect of heating bicarbonate of ammonia in remained ammonia system by Mg and Zn respectively with MgCO
3and ZnCO
3precipitation forms is removed, the spent acid that then adds again cold-rolling process to produce, and before the spent acid that adds cold-rolling process to produce, in system, bismuth element is mainly to comprise Bi
2o
3, Bi
2s
3and the existence of the form of simple substance Bi, add after spent acid, can mainly there is following reaction:
Fe
2O
3+H
+→Fe
3++H
2O
Bi
2O
3+HCl→BiCl
3+H
2O
Bi
2s
3+ Fe
3+→ Bi
3++ Fe
2++ S (precipitation)
Bi+Fe
3+→Bi
3++Fe
2+；
And make in system soluble for sour metallic impurity elements comprise ferro element corresponding with manganese element with ionic species as Fe
2+, Fe
3+, Mn
2+, Mn
4+deng existence, and because bismuth sulfate is soluble in hydrochloric acid, the Bi element in system can not separated out with bismuth sulfate precipitation forms from system, and mainly with Bi
3+form exists.In addition in this course, the lead element in system can be with PbSO
4precipitation forms is separated out (because it is insoluble to HCl, and bismuth is quite different).The salkali waste that adds afterwards cold-rolling process to produce can make the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+correspondingly with precipitation forms, remove, wherein Fe
2+, Fe
3+mainly with Fe (OH)
2, Fe (OH)
3deng precipitation forms, separate out, and Mn (OH) in system
2and Mn (OH)
4unstable, can finally transform with MnO
2deng precipitation forms, separate out; Last again by the pH of regulation system, the system pH of making remains between 1.5 ~ 2.1, thereby makes the Cl in system
-and Bi
3+common hydrolytic action generates BiOCl precipitation, then filters and get final product, and the reaction now occurring is as follows: BiCl
3+ H
2o=BiOCl ↓+2 HCl.
Beneficial effect of the present invention: with low cost, can very economically from gas mud, reclaim precious metal bismuth and make BiOCl;
Can realize the second stage employ of coke-oven plant's coking process remained ammonia, reduce the pollution of residual coking ammonia water to environment;
Realize the spent acid of the cold rolling industry generation of iron and steel and the second stage employ of salkali waste, save the control expense of spent acid and salkali waste.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention 1.
Embodiment
Embodiment 1
From gas mud, reclaim bismuth and prepare a technique of BiOCl, as shown in Figure 1, step is as follows:
(1) get blast furnace gas mud 1Kg, add the remained ammonia 5L that coking process produces, more than soaking 30min, with dissolve can and NH
3the impurity element of complexing comprises Cu, Ag, Ni, Co;
(2) in above-mentioned immersion system, add 10g Mg powder, the ammonia complex that comprises Cu, Ag, Ni, Co than the metallic impurity elements of its poor activity is replaced into corresponding simple substance form by replacement(metathesis)reaction, remove by filter;
(3) slowly heating, makes system temperature rise to 120 ℃, and keeps 50min, and makes the corresponding MgCO of being converted under the acting in conjunction of magnesium elements in system and zinc element bicarbonate of ammonia in residual coking ammonia water
3precipitation or ZnCO
3precipitation forms, filters and removes;
(4) the spent acid 3L that adds cold-rolling process to produce, makes lead element in system with PbSO
4precipitation forms is removed, make simultaneously in system soluble for sour metallic impurity elements comprise ferro element and manganese element with ionic species as Fe
2+, Fe
3+, Mn
2+, Mn
4+exist, make bismuth element with Bi
3+form exists;
(5) the salkali waste 3L that adds cold-rolling process to produce, makes the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+corresponding to Fe (OH)
2, Fe (OH)
3, MnO
2deng precipitation forms, separate out, remove by filter;
(6) with HCl regulation system pH, the system pH of making remains between 1.5 ~ 2.1, thereby makes the Cl in system
-and Bi
3+common hydrolytic action generates white precipitate, and it is BiOCl that filtration washing obtains white crystalline material.
Embodiment 2
From gas mud, reclaim bismuth and prepare a technique of BiOCl, step is as follows:
(1) get blast furnace gas mud 1Kg, add the remained ammonia 4L that coking process produces, soak 1h, with dissolve can and NH
3the impurity element of complexing comprises Cu, Ag, Ni, Co;
(2) in above-mentioned immersion system, add 6g Mg powder, the ammonia complex that comprises Cu, Ag, Ni, Co than the metallic impurity elements of its poor activity is replaced into corresponding simple substance form by replacement(metathesis)reaction, remove by filter;
(3) slowly heating, makes system temperature rise to 100 ℃, and keeps 30min, and makes the corresponding MgCO of being converted under the acting in conjunction of magnesium elements in system and zinc element bicarbonate of ammonia in residual coking ammonia water
3precipitation or ZnCO
3precipitation forms, filters and removes;
(4) the spent acid 2L that adds cold-rolling process to produce, makes lead element in system with PbSO
4precipitation forms is removed, make simultaneously in system soluble for sour metallic impurity elements comprise ferro element and manganese element with ionic species as Fe
2+, Fe
3+, Mn
2+, Mn
4+exist, make bismuth element with Bi
3+form exists;
(5) the salkali waste 2L that adds cold-rolling process to produce, makes the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+corresponding to Fe (OH)
2, Fe (OH)
3, MnO
2deng precipitation forms, separate out, remove by filter;
(6) use HNO
3regulation system pH, the system pH of making remains between 1.5 ~ 2.1, thereby makes the Cl in system
-and Bi
3+common hydrolytic action generates white precipitate, and it is BiOCl that filtration washing obtains white crystalline material.
Embodiment 3
From gas mud, reclaim bismuth and prepare a technique of BiOCl, step is as follows:
(1) get gas mud 1Kg, add the remained ammonia 6L that coking process produces, fully soak, with dissolve can and NH
3the impurity element of complexing comprises Cu, Ag, Ni, Co;
(2) in above-mentioned immersion system, add 12g Mg powder, the ammonia complex that comprises Cu, Ag, Ni, Co than the metallic impurity elements of its poor activity is replaced into corresponding simple substance form by replacement(metathesis)reaction, remove by filter;
(3) heating, makes system temperature rise to 100 ℃, and keeps 30min, and makes the corresponding MgCO of being converted under the acting in conjunction of magnesium elements in system and zinc element bicarbonate of ammonia in residual coking ammonia water
3precipitation or ZnCO
3precipitation forms, filters and removes;
(4) the spent acid 4L that adds cold-rolling process to produce, makes lead element in system with PbSO
4precipitation forms is removed, make simultaneously in system soluble for sour metallic impurity elements comprise ferro element and manganese element with ionic species as Fe
2+, Fe
3+, Mn
2+, Mn
4+exist, make bismuth element with Bi
3+form exists;
(5) the salkali waste 4L that adds cold-rolling process to produce, makes the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+corresponding to Fe (OH)
2, Fe (OH)
3, MnO
2deng precipitation forms, separate out, remove by filter;
(6) use HNO
3regulation system pH, the system pH of making remains between 1.5 ~ 2.1, thereby makes the Cl in system
-and Bi
3+common hydrolytic action generates white precipitate, and it is BiOCl that filtration washing obtains white crystalline material.
Claims (8)
1. from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: it comprises the following steps:
(1) get gas mud, add remained ammonia that coking process produces soak to dissolve can and NH
3the impurity element of complexing comprises Cu, Ag, Ni, Co;
(2) in above-mentioned immersion system, add Mg powder, the ammonia complex that comprises Cu, Ag, Ni, Co than the metallic impurity elements of its poor activity is replaced into corresponding simple substance form by replacement(metathesis)reaction, remove by filter;
(3) heating, makes the corresponding MgCO of being converted under the acting in conjunction of magnesium elements in system and zinc element bicarbonate of ammonia in residual coking ammonia water
3or ZnCO
3precipitation forms, removes by filter;
(4) spent acid that adds cold-rolling process to produce, makes lead element in system with PbSO
4precipitation forms is removed, and makes solublely in system for sour metallic impurity elements comprises that ferro element is corresponding with manganese element, with ionic species, to exist simultaneously, comprises Fe
2+, Fe
3+, Mn
2+, Mn
4+, make bismuth element with Bi
3+form exists;
(5) salkali waste that adds cold-rolling process to produce, makes the metallic impurity ion in system comprise Fe
2+, Fe
3+, Mn
2+, Mn
4+corresponding Precipitation, removes by filter;
(6) regulation system pH is 1.5 ~ 2.1, makes the Cl in system
-and Bi
3+common hydrolytic action generates BiOCl precipitation aftertreatment and get final product.
2. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: the needed remained ammonia amount of every 1Kg gas mud is 4 ~ 6 L, soak duration and be at least 30min.
3. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: the needed Mg powder content of every 1Kg gas mud is 6 ~ 12g.
4. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: described step (3) is 80 ~ 120 ℃ for system is slowly heated to system temperature, keep 30 ~ 50 min, so that the corresponding MgCO that is converted into of the magnesium elements in system and zinc element
3or ZnCO
3precipitation forms, removes by filter.
5. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: the consumption of the spent acid that the needed cold-rolling process of every 1Kg gas mud produces is 2 ~ 4L.
6. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: the consumption of the salkali waste that the needed cold-rolling process of every 1Kg gas mud produces is 2 ~ 4L.
7. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: the pH adjusting agent in described step (6) is nitric acid or hydrochloric acid.
8. according to claim 1ly from gas mud, reclaim the technique that bismuth is prepared BiOCl, it is characterized in that: described gas mud is blast furnace gas mud.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210546124.0A CN103014349B (en) | 2012-12-14 | 2012-12-14 | Process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210546124.0A CN103014349B (en) | 2012-12-14 | 2012-12-14 | Process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride) |
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|---|---|
| CN103014349A CN103014349A (en) | 2013-04-03 |
| CN103014349B true CN103014349B (en) | 2014-04-23 |
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| CN201210546124.0A Expired - Fee Related CN103014349B (en) | 2012-12-14 | 2012-12-14 | Process for recycling bismuth from gas sludge to prepare BiOCl (Bismuth Oxychloride) |
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| CN100557045C (en) * | 2007-06-23 | 2009-11-04 | 王树楷 | From blast furnace dust, extract the method for indium metal, zinc, bismuth |
| CN101289171B (en) * | 2008-06-02 | 2010-06-02 | 王钧 | Hydrometallurgy process for abstracting 99.99% Te and 99.99% Bi2O3 and comprehensively recovering accessory products |
| CN102031383B (en) * | 2010-11-28 | 2012-07-25 | 郴州市金贵银业股份有限公司 | Wet process for lead-silver residues |
| CN102650000A (en) * | 2012-04-28 | 2012-08-29 | 中南大学 | Method for recovering bismuth and arsenic from bismuth and arsenic-containing solution |
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Effective date of registration: 20170712 Address after: 430083, Gate No. 2, Qingshan District, Hubei, Wuhan Patentee after: Wuhan iron and Steel Company Limited Address before: 430080 Wuhan, Hubei Friendship Road, No. 999, Wuchang Patentee before: Wuhan Iron & Steel (Group) Corp. |
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